New bis-naphthoxazolyl-derivatives

ABSTRACT

WHEREIN U denotes a diphenyl radical bonded in the 4,4&#39;&#39;-position to the oxazole rings and U1 and U2 denote naphthalene radicals fused to the oxazole rings, and wherein up to four positions capable of substitution in U; U1 and U2 can be substituted with optionally substituted alkyl groups, halogen or optionally functionally modified sulphonic acid groups and up to 2 positions capable of substitution can be substituted with optionally substituted phenyl groups, phenylalkyl groups, -SO2-phenyl, nitrile or optionally functionally modified carboxyl groups. The naphthoxazole compounds are useful as optical brightening agents.   The present invention relates to new azole derivatives of the naphthoxazole type which in the most general case correspond to the formula

United States Patent Liechti [151 3,682,946 [451 Aug. 8, 1972 [54] NEWBIS-NAPHTHOXAZOLYL- DERIVATIVES [22] Filed: March 2, 1970 [21] Appl.No.: 15,912

[30] Foreign Application Priority Data March 6, 1969 Switzerland..,...3406/69 [52] 11.8. CI. ..260/307 D, 252/3012 W [51] Int. Cl...C07d 85/48 [58] Field of Search ..260/307 D [56] References CitedFOREIGN PATENTS OR APPLICATIONS 11,247 5/1968 Japan PrimaryExaminer-Alex Mazel Assistant Examiner-R. V. Rush Attorney-HarryGoldsmith, Joseph G. Kolodny and Mario A. Monaco [5 7] ABSTRACT Thepresent invention relates to new azole derivatives of the naphthoxazoletype which in the most general case correspond to the formula wherein Udenotes a diphenyl radical bonded in the 4,4-position to the oxazolerings and U and U denote naphthalene radicals fused to the oxazolerings, and wherein up to four positions capable of substitution in U; Uand U can be substituted with optionally substituted alkyl groups,halogen or optionally functionally modified sulphonic acid groups and upto 2 positions capable of substitution can be substituted withoptionally substituted phenyl groups, phenylalkyl groups, SO -phenyl,nitrile or optionally functionally modified carboxyl groups. Thenaphthoxazole compounds are useful as optical brightening agents.

4 Claims, No Drawings 1 NEW BIS-NAPHTHOXAZOLYL-DERIVATIVEQ SPECIFICEMBODIMENTS Within the framework of Formula (1), those com- 5 pounds areabove all of interest which correspond to the general formula O\ /o 1 X)Te).

wherein A and B can be identical or diflerent and each denotes a benzenering fused onto the benzoxazole ring system, X denotes hydrogen or analkyl group which contains one to 18 C atoms and is optionally furthersubstituted, halogen or a group SO Z, Y represents hydrogen or a phenylgroup, phenylalkyl(one to four C) group, an SO -phenyl group or a COZgroup, wherein Z denotes the group OH, OMe (Me cation of a water-solublesalt), OR, NHR or N(R) and R represents an alkyl group containing up to12 C atoms or a phenylalkyl (one to four C) or phenyl group, m denotesan integer from 1 to 4, n denotes an integer from 1 to 2 and the sum m+n is not greater than 4.

The opened rings with the symbols A and B, con- As expressed by thebracket, the substituents X and do not have more than 4 C atoms in thealkyl part.

Compounds of preferred significance within the framework of Formula (1)are those which correspond to the formula 25 wherein A denotes a benzenering fused onto the wherein A denotes a benzene ring fused onto thebenzoxazole ring system, X denotes hydrogen, an alkyl group containingone to four carbon atoms, chlorine or the group SO Z, wherein Zrepresents the group OH, OMe (Me cation of a water-soluble salt), OR,NHR or N(R) and R represents an alkyl group containing up to 12 carbonatoms, or a phenylalkyl (one to four C) or phenyl group, and n denotesthe numbers 1 or 2.

Compounds of preferred significance are the subgroup of naphthoxazolecompounds of Formula (1), to which the unsubstituted base substance andthe lower sulphonic acid derivatives belong. These compounds canaccordingly be described by the following Formu- Y can be present bothin the naphthoxazole radicals 55 lae (5) and (6):

and also in the central diphenylyl grouping.

together all inherently customary substitution possibilities in alkylgroups, that is to say for example hydroxyalkyl, alkoxyalkyl,carboxyalkyl, carbalkoxyalkyl,

Compounds of formula wherein A denotes a benzene ring fused (inpositions 4:5, 5:6 or 6:7) to the benzoxazole ring system, X

65 represents hydrogen or a sulphonic acid group as' well \C C/0 IJIN ,1@Q \N/ wherein X represents hydrogen or a sulphonic acid 0 O uil whereinW represents a hydroxyl group, an alkoxy group or a halogen atom,especially a chlorine atom and the diphenyl nucleus U can be substitutedin the sense of Formula (1), with an o-amino compound of formula inaccordance with the following scheme:

i ii U1 C U C W1 OAlkyl NHz l -HW1 J-U( i\ NH/ O-A1kyl l -Hz O 0 l H U10 UC OAlky1 Thereafter, the alkyl ester group of the azole compound ofFormula (10) is optionally saponified to give the carboxyl group,optionally converted into a carboxylic acid halide group, especiallycarboxylic acid chloride group, and the compound of formula nowobtained, wherein W, has the significance given in conjunction withFormula (7), is reacted with an 0- amino compound of formula lI'JNwherein U, U and U have the initially indicated significance, inaccordance with the following reaction scheme:

Bis-azole compound of Formula 1).

Bis-azoles of Formula (3) are appropriately manufactured by condensingabout 2 mols of an aminophenol of formula A l NH:

with about 1 mol of a compound of formula and bringing about oxazolecyclization, by heating to temperatures above C in the presence ofagents which split off water, with A and R in the above formulae havingthe abovementioned significance and W 0 o W1-(HJ- (IJJW1 wherein W;represents a hydroxyl group, an alkoxy group or a halogen atom,especially a chlorine atom,

are reacted in a molecular ratio of 1:2 with o-amino compounds offormula in accordance the following reaction scheme:

Qolnpound of formula (4) The reaction between the particular componentsof Formulae (7) and (8), (l 1) and 12), (14) and 15), as well as (16)and (17) can be carried out with or without intermediate separation ofthe acylamino compounds of Formulae (9), (l3), (18) or the like firstproduced, by heating to higher temperatures, for example to 120-350C,advantageously in an inert gas, for example in a stream of nitrogen,with the reaction optionally being carried out in the presence of acatalyst. Suitable catalysts are for example boric acid, boric acidanhydride, zinc chloride, p-toluenesulphonic acid and alsopolyphosphoric acid, including pyrophosphoric acid. If boric acid isused as the catalyst, then this is advantageously used in an amount of0.5 to percent relative to the total weight of the reaction mass. It isalso possible conjointly to use high-boiling polar organic solvents,such as for example dimethylformamide, dichlorobenzene, trichlorobenzeneand aliphatic optionally etherified hydroxyl compounds, for examplepropylene glycol, ethylene glycol monoethyl ether or diethylene glycoldiethyl ether, as well as high-boiling esters of phthalic acid, such asfor example dibutyl phthalate.

Preferably, however, the process is carried out in two steps, by firstcondensing the carboxylic acid halides, especially carboxylic acidchlorides of Formulae (7), (ll), or 16) with the o-amino compoundsofformulae (8), (l2), (14), or 17) in the presence ofan organic inertsolvent such as toluene, xylenes, chlorobenzene, dichlorobenzene,trichlorobenzene or nitrobenzene at temperatures between 100 and 200Cand subjecting the resulting acyl compounds of Formulae (9), (l3), and(18) at temperatures above 100C, preferably between 120 and 350C, and inthe presence of a catalyst which splits off water, to the cyclizationreaction to form the azole derivatives. If carboxylic acid chlorides areused as starting sub stances, then these can be manufactured directlybefore the condensation with the o-amino compound and without isolationfrom the free carboxylic acid and thionyl chloride, optionally with theaddition of a catalyst such as pyridine, in the solvent wherein thesubsequent condensation takes place.

themselves customary, (for example concentrated sulphuric acid, oleumand the like). The sulphonic acid derivatives thus obtained (forexample, disulphonic acid according to Formula 25) can be used asbrighteners for cotton.

Furthermore, alkyl and acyl groups can be produced by Friedel-Craftsreactions, or subsequent chloralkylations or chlorinations can becarried out.

A further route to water-soluble derivatives of Formula 1) consists offurther reacting sulphochlon'des or carboxylic acid chlorides of Formula(1) with such alcohols or amines as contain groups which confersolubility in water or groups which can be converted into suchgroups-for example by quatemization-such as sulphonic acid groups andamino groups.

Furthermore, water-soluble derivatives of Formula (1) can also beobtained by converting halogenalkyl groups into the correspondingquaternary derivatives by means of tertiary bases.

The new compounds defined above possess a more or less pronouncedfluorescence in the dissolved or finely divided state. They can be usedfor the optical brightening of the most diverse synthetic, semisyntheticor natural organic materials or substances which contain such organicmaterials.

As examples thereof, the following groups of organic materials may bementioned, to the extent that optical brightening of these is possible,without the survey which follows being intended to express anyrestriction thereupon:

1. Synthetic organic high molecular materials:

a. Polymerization productsbased on organic compounds containing at leastone polymerizable carboncarbon double bond, that is to say theirhomopolymers or copolymers as well as their post-treatment products suchas for example crosslinking, grafting or degradation products, polymerdilutions, products obtained by modification of reactive groups, and thelike, such as for example polymers based on call-unsaturated carboxylicacids or derivatives of such carboxylic acids, especially on acryliccompounds (such as for example acrylic esters, acrylic acid,acrylonitrile, acrylamides and their derivatives or their methacrylicanalogues),

obtainable by ring opening, for example, polyamides of thepolycaprolactam type, also polymers which are obtainable both viapolyaddition and polycondensation, such as polyethers or polyacetals.

c. Polycondensation products or precondensates based on bifunctional orpolyfunctional compounds possessing condensable groups, theirhomo-condensation and co-condensation products as well as products ofpost-treatment, such as for example polyesters, saturated (for examplepolyethylene glycol terephthalate) or unsaturated (for example maleicacid-dialcohol polycondensates as well as their crosslinking productswith copolymerizable vinyl monomers), unbranched as well as branched(also based on polyhydric alcohols, such as for example alkyd resins),polyamides (for example, hexamethylenediamine adipate), maleate resins,melamine resins, polycarbonates, and silicones.

d. Polyaddition products such as polyurethanes (cross-linked anduncrosslinked) and epoxide resins.

II. Semi-synthetic organic materials such as for example celluloseesters of various degrees of esterification or mixed esters (acetate ortriacetate), cellulose ethers, regenerated cellulose (viscose, orcuprammonium-cellulose) or their post-treatment products, and caseinplastics.

111. Natural organic materials of animal or vegetable origin, forexample based on cellulose or proteins, such as cotton, wool, linen,silk, natural lacquer resins, starch and casein.

The organic materials to be optically brightened can be in the mostdiverse processing states (raw materials, semi-finished goods orfinished goods). They can also be in the form of structures of the mostdiverse shapes, that is to say for example predominantlythree-dimensional articles such as sheets, profiles, injection mouldingsor the most diverse articles for working, chips or granules, or foams,as predominantly twodimensional articles such as films, foils, lacquers,coverings, impregnations and coatings, or as predominantlyone-dimensional articles such as filaments, fibers, flocks or wires. Thesaid materials can on the other band also be in unshaped states, in themost diverse homogeneous or inhomogeneous forms of division, for examplein the form of powders, solutions, emulsions, dispersions, latices,pastes, or waxes.

Fiber materials can for example be in the form of continuous filaments,staple fibers, flocks, hanks, textile filaments, yarns, threads, fiberfleeces, felts, waddin gs, flocked structures or woven textile fabricsor textile laminates, knitted fabrics as well as papers, cardboards orpaper compositions and the like.

The compounds to be used according to the invention are also ofimportance for the treatment of organic textile materials, especiallywoven textile fabrics. Where fibers, which can be in the form of staplefibers or endless filaments, hanks, woven fabrics, knitted fabrics,fleeces, flocked substrates or laminates, are to be optically brightenedaccording to the invention, this is advantageously done in an aqueousmedium, wherein h the compounds in question are present in a finelydivided form (suspensions, or optionally solutions). in the treatment,dispersing agents can optionally be added, such as for example soaps,polyglycol ethers of fatty alcohols, fatty amines or alkylphenols,cellulose sulphite waste lye or condensation products of optionallyalkylated naphthalene-sulphonic acids with formaldehyde. It has provedparticularly appropriate to carry out the process in a neutral, weaklyalkaline or acid bath. it is also advantageous if the treatment iscarried out at elevated temperatures of about 50 to 100C, for example atthe boiling point of the bath or near to this (about C). For thefinishing process according to the invention it is also possible to usesolutions in organic solvents, as is practised in so-called solventdyeing (paddenthermofixing application, ex-

haustion dyeing process in drum dyeing machines), for example, forpolyamide and polyester substrates.

The new optical brighteners according to the present invention canfurthennore be added to, or incor porated in, the materials before orduring their shaping. Thus they can, for example, be added to thecompression molding composition when manufacturing films, sheets (forexample milling into hot polyvinyl chloride) or moldings. in the case ofspinning compositions (fully synthetic or semi-synthetic materials) theoptical brighteners can be added to the starting substances (forexample, monomers), the intermediate products (for example, dusting ontopolymer chips or granules) or the spinning melts or spinning solutions.

The amounts of the new optical brighteners to be used according to theinvention, relative to the material to be optically brightened, can varywithin wide limits. A distinct and lasting efiect can already beachieved with very small amounts, in certain cases for example amountsof 0.001 percent by weight. it is however also possible to employamounts of up to about 0.5 percent by weight and above. For mostpractical purposes, amounts between 0.01 and 0.2 percent by Weight arepreferably of interest.

The optical brighteners according to the present invention can forexample also be employed in the fol- I lowing use forms:

a. Wxed with dyestufi's (shading) or pigments (for example, whitepignents), or as an additive to dyebaths or printing, etching or reservepastes. Also for the aftertreatment of dyeings, prints or dischargeprints.

b. Mixed with so-called carriers, wetting agents, plasticizers, swellingagents, antioxidants, light protec tion agents, heat stabilizers andchemical bleaching agents (bleaching bath additives).

c. Mixed with crosslinking agents and finishing agents (for examplestarch or synthetic finishes), and in combination with the most diversetextile finishing processes, especially synthetic resin finishes (forexample, wash and wear, permanent press, no iron," flameproof finishes,soft handle finishes, creaseproof finishes or antistatic finishes).

d. In combination with detergents. The detergents and brighteners can beseparately added to the wash liquors which are to be used. it is alsoadvantageous to use detergents which contain the brighteners as anadmixture. Suitable detergents are for example soaps, salts ofsulphonate detergents, such as for example of sulphonated benzimidazoleswhich are substituted by higher alkyl radicals at the 2-carbon atom, andalso salts of monocarboxylic acid esters of 4-sulphophthalic acid withhigher fatty alcohols, as well as salts of fatty alcohol sulphonates,alkylarylsulphonic acids or condensation products of higher fatty acidswith aliphatic hydroxysulphonic or aminosulphonic acids. Non-ionicdetergents can furthermore be employed, for example, polyglycol ethersderived from ethylene oxide and higher fatty alcohols, alkylphenols orfatty amines.

e. Incorporation of the optical brighteners into polymeric carriers(polymerization, polycondensation or polyaddition products) in thedissolved or dispersed form, or use, for example, with coating agents,impregnating agents or binders (solutions, dispersions or emulsions) fortextiles, fleeces, paper or leather.

f. As additives to so-called master batches.

g. As additives to the most diverse industrial products in order to makethese more marketable (for example, improving the appearance of soaps,detergents and the like).

h. In combination with other optically brightening substances.

i. In spinning bath preparations, that is to say as additives tospinning baths such as are used for improving the slip for the furtherprocessing of synthetic fibers.

k. As scintillators for various purposes of a photographic nature suchas for example for electrophotographic reproduction orsupersensitization.

If the brightening process is combined with textile treatment orfinishing methods, the combined treatment is in many casesadvantageously carried out with the aid of appropriate stablepreparations which contain the optically brightening compounds in suchconcentrations that the desired brightening effect is achieved.

When treating a series of fiber substrates, for example of polyesterfibers, with the brighteners according to the invention, the appropriateprocedure is that these fibers are impregnated with the aqueousdispersions of the brighteners at temperatures below 75C, for example,at room temperature, and subjected to a dry heat treatment attemperatures above 100C, it being generally advisable still to dry thefiber material beforehand at a moderately elevated temperature, forexample at minimally 60 to about 100C. The heat treatment in the drystate is then advantageously carried out at temperatures between 120 and225C, for example, by warming in a drying chamber, by ironing in thespecified temperature range or by treatment with dry superheated steam.The drying and dry heat treatment can also be carried out in immediatesuccession to one another or be combined into a single working sta e.

1% the examples, parts, unless otherwise stated, are always parts byweight and percentages always percentages by weight. Unless otherwisestated, melting points and boiling points are uncorrected.

EXAMPLE 1 A mixture of 12.1 g of diphenyl-4,4-dicarboxylic acid, 15.9 gof 1-amino-2-naphthol, 0.25 g of boric acid, 7.9 g of pyridine and 100 gof a mixture of 73 percent of diphenyl-ether and 27 percent of diphenylis heated to a temperature of 250C over the course of about 7 hours in astream of nitrogen whilst stirring, in the course of which pyridine, thewater formed and a little diphenyl/diphenyl-ether mixture distil off.After cooling, filtering off, washing with alcohol and drying, 15.8 g ofthe crude compound of formula l 1 r N are obtained as a brown-yellowpowder. Repeated recrystallization from dichlorobenzene, using Fullersearth, yields light yellow crystals of melting point 349 to 351C.

C H O N l/ 5 dichlorobenzene Calculated: C 81.4 H 4.1 N 5.4 Cl 2.7

Found: C 81.4 H 4.4 N 5.8 Cl 2.9

EXAMPLE 2 4.64 g of 4,4-dicyano-3,3-dimethyl-diphenyl and 6.35 g ofl-amino-2-naphthol in 50 g of polyphosphoric acid are heated to C overthe course of 3 hours in a stream of nitrogen, whilst stirring, and keptfor 1 hour at 180 to C. After cooling, 70 ml of water are added and thecompound of formula I I i J N (5 N I is filtered off, washed with waterand dried. 1 1.0 g of a brown powder are obtained, which can be purifiedby chromatography on aluminum oxide (activity I according to Brockmann)with tetrachlorethylene as the eluting agent, and recrystallization fromodichlorobenzene, to give light yellow crystals of melting point 288 to290C.

Calculated: C 83.70 H 4.68 N 5.42

Found: C 83.75 H 4.74 N 5.44

EXAMPLE 3 /O\C h I WO/(KA /\N/ Q kl vll are obtained as a yellow-brownsubstance. After chromatography on aluminum oxide (activity 1 accordingto Brockmann) with methylene chloride as the eluting agent, andsubsequent recrystallization from odichlorobenzene, greenish-yellowcrystals of melting point 357 to 358C are obtained.

C34H2002N2 5 dichlol'Obenzene I Calculated: C 81.4 H 4.1 N 5.4 Found: C81.6 H 4.1 N 5.5.

EXAMPLE 4 13.95 g of diphenyl-4,4-dicarboxylic acid dichloride and 15.9g of 2-amino-3-naphthol in 125 ml of trichlorobenzene are heated in astream of nitrogen whilst stirring, to 190C over the course of 3 hoursand in 200 ml of 95 percent strength sulphuric acid are stirred forminutes at 80 to 90C. After cooling, the resulting greenish-brownsolution is poured onto 500 g of ice and the precipitate is filteredoff, washed with methanol and dried in vacuo at 80C. 9.5 g of thecompound of formula EXAMPLE 6 Hundred parts of polyester granules of to210C over the course of a further 2 hours. The com- 25 polyterephthalicacid ethylene glycol ester are intipound of formula mately mixed with0.05 part of the compound of For- (22 on i no O 0 U I x5 \4 hereuponforms, with hydrogen chloride being split off. The yellow product (26.1g) is filtered off, washed with carbon tetrachloride and dried. Meltingpoint 360C.

5.24 g of this amide (crude product) are heated to 330C with 0.2 g ofboric acid anhydride in ml of dibutyl phthalate, in the course of whichthe water formed, and a little solvent, distil off and an almost clearsolution is produced. The mixture is allowed to 4 cool and the compoundof formula which has crystallized out is filtered off, washed withalcohol and dried in vacuo at C. 3.2 g of light green 50 crystals areobtained. Recrystallization from trichlorobenzene with the aid ofFullers earth yields light yellow crystals which do not melt below 360C.

Calculated: C 83.59 H 4.13 N 5.73

Found: C 83.18 H 4.31 N 5.22

EXAMPLE 5 10.0 g of the compound of formula /o\cw c/o\ Q Q (N) EXAMPLE 7Ten thousand pans of a polyamide, manufactured from hexamethylenediamineadipate in a known manner, in chip form are mixed with 30 parts oftitanium dioxide (rutile modification) and 10 parts of the compound ofFormula (19), (20) or (21) in a tumbler vessel for 12 hours. The chipstreated in this way are melted, after displacement of the atmosphericoxygen by superheated steam, in a kettle heated to 3003 10C by means ofoil or diphenyl vapor, and stirred for half an hour. The melt isthereafter extruded under a nitrogen pressure of atmospheres gaugethrough a spinneret, and the filament which has been spun in this 2. Anazole compound according to claim 1 which corresponds to the formulafect, which is stable to thermofixing, and has good fastness to washingand light.

EXAMPLE 8 Ten thousand parts of a polyarnide, manufactured frome-caprolactam in a known manner, in chip form are mixed for 12 hourswith 30 parts of titanium dioxide (rutile modification) and two parts ofthe compound of formula (19), (20) or (21) in a tumbler vessel. Thechips treated in this way are melted, after displacement of theatmospheric oxygen, in a kettle heated to 270C and stirred for half anhour. The melt is thereafter extruded through a spinneret under anitrogen pressure of 5 atmospheres gauge and the cooled filament iswound on a spinning bobbin. The resulting filaments show an excellentbrightening effect which is resistant to thermofixing and has goodfastness to washing and light.

I claim: 1. An azole compound which corresponds to the formula wherein Adenotes a benzene ring fused onto the benzoxazole ring system and Rrepresents a member selected from the group consisting of hydrogen andan alkyl group container one to four carbon atoms.

wherein A denotes a benzene ring fused onto the benzoxazole ring system.

3. An azole compound according to claim 1 which corresponds to theformula 4. The product containing one or two sulfonic acid groupsobtained by sulfonating with concentrated sulfuric acid or oleum acompound of the formula n R X QQN/ QKNIQQ wherein A denotes a benzenering fused onto the benzoxazole ring system and R, represents a memberselected from the group consisting of hydrogen and an alkyl groupcontaining one to four carbon atoms.

* I 'I I UNITED STATES PATENT OFFICE CERTIMCATE 0F coRREe'HoN Patent No.3.682.9 5 Dated August 8, Q 972 Inventor-(s) PETER LIECHTI It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Cover page,- after [73] Assigne'ez" delete "Ciba-Geigy" and insert -e--CIBA-GEIGY AG, Basle Switzerland Signed and sealed this 23rd day ofApril 197k.

(SEAL) Attest:

EDWARD I LFLETGHERJR. C. l-IARSHALL DANE-I Commissioner of Patents Attesting; Officer

2. An azole compound according to claim 1 which corresponds to theformula
 3. An azole compound according to claim 1 which corresponds tothe formula
 4. The product containing one or two sulfonic acid groupsobtained by sulfonating with concentrated sulfuric acid or oleum acompound of the formula